The invention relates to a dye composition for keratin fibers, especially for human keratin fibers such as the hair, comprising, in a medium suitable for dyeing, at least one cationic direct dye of given formula, and at least one specific cationic or amphoteric substantive polymer.
The invention also relates to the dyeing processes and devices using said composition.
Two types of dyeing processes can be distinguished in the field of hair treatment. The first type of dyeing process is semi-permanent or temporary dyeing, or direct dyeing, which involves dyes capable of giving the hair""s natural colour a more or less pronounced colour change that may withstand shampooing several times. These dyes are known as direct dyes; they can be used with or without an oxidizing agent. In the presence of an oxidizing agent, the aim is to obtain a lightening coloration. The lightening coloration is carried out by applying a mixture, prepared at the time of use, of a direct dye and an oxidizing agent to the hair. This mixture makes it possible to obtain, by lightening the melanin in the hair, an advantageous effect such as unifying the colour in the case of grey hair, or bringing out the colour in the case of naturally pigmented hair.
The second type of dyeing process is permanent dyeing or oxidation dyeing. This dyeing is carried out with dyes known as xe2x80x9coxidationxe2x80x9d dyes comprising oxidation dye precursors and couplers. Oxidation dye precursors, commonly known as xe2x80x9coxidation bases,xe2x80x9d are initially colourless or weakly coloured compounds that develop their dyeing power on the hair in the presence of oxidizing agents added at the time of use, leading to the formation of coloured compounds and dyes. The formation of these coloured compounds and dyes results either from an oxidative condensation of the xe2x80x9coxidation basesxe2x80x9d with themselves, or from an oxidative condensation of the xe2x80x9coxidation basesxe2x80x9d with coloration modifier compounds commonly known as xe2x80x9ccouplers,xe2x80x9d which are generally present in the dye compositions used in oxidation dyeing.
To vary the shades obtained with the oxidation dyes, or to enrich them with glints, it is known to add direct dyes thereto.
Among the cationic direct dyes available in the field of dyeing keratin fibres, especially human keratin fibres, compounds which are already known are those whose structure is developed in the following text; nevertheless, these dyes have insufficient coloration properties, both with regard to the homogeneity of the colour distributed along the fibre (xe2x80x9cunisonxe2x80x9d), where it is said that the coloration is too selective, and with regard to the staying power, or resistance to the various attacking factors to which the hair may be subjected (light, bad weather, shampooing).
After considerable research conducted in this field, the Applicants have now discovered that it is possible to obtain novel compositions for dyeing keratin fibres, which are capable of leading to less selective colorations and which are particularly resistant to the various attacking factors to which the hair may be subjected, by combining at least one specific cationic or amphoteric substantive polymer with at least one cationic direct dye known in the prior art and of formula (I) defined below.
This discovery forms the basis of the present invention.
Additional features and advantages of the invention are set forth in the description that follows, and, in part, will be apparent from the description or may be learned from the practice of the invention. The advantages of the invention will be realized and attained by the dyeing compositions, processes, and kits particularly pointed out in the written description and claims.
Both the foregoing general description and the following detailed description of the invention are exemplary and explanatory only and are not restrictive of the claimed invention.
A first subject of the present invention is, therefore, a composition for dyeing keratin fibres, especially human keratin fibres such as the hair, comprising, in a medium suitable for dyeing, (i) at least one cationic direct dye whose structure corresponds to formula (I) below, further comprising (ii) at least one specific cationic or amphoteric substantive polymer.
(i) The cationic direct dye which can be used according to the present invention is a compound of formula (I) below:
Axe2x80x94Nxe2x95x90Nxe2x80x94Bxe2x80x83xe2x80x83(1)
in which: the symbol A represents a group selected from structures A1 to A3 below: 
in which structures A1 to A3,
R1 represents a C1-C4 alkyl radical, a phenyl radical which can be substituted with a C1-C4 alkyl radical or a halogen atom selected from chlorine, bromine, iodine and fluorine;
R2 represents a C1-C4 alkyl radical or a phenyl radical;
R3 and R4, which may be identical or different, represent a C1-C4 alkyl radical, a phenyl radical or, in the case of structure A1, can together form a substituted benzene ring, and in the case of structure A2, can together form a benzene ring optionally substituted with one or more C1-C4 alkyl, C1-C4 alkoxy or NO2 radicals;
R3 can also represent a hydrogen atom;
Z represents an oxygen or sulphur atom or a group xe2x80x94NR2;
M represents a group xe2x80x94CH, xe2x80x94CR (R denoting C1-C4 alkyl) or xe2x80x94NR5(Xxe2x88x92)r;
K represents a group xe2x80x94CH, xe2x80x94CR (R denoting C1-C4 alkyl) or xe2x80x94NR5(Xxe2x88x92)r;
P represents a group xe2x80x94CH, xe2x80x94CR (R denoting C1-C4 alkyl) or xe2x80x94NR5(Xxe2x88x92)r; r represents 0 or 1;
R5 represents an atom Oxe2x88x92, a C1-C4 alkoxy radical or a C1-C4 alkyl radical;
R6 and R7, which may be identical or different, represent a hydrogen atom or a halogen atom selected from chlorine, bromine, iodine and fluorine, a C1-C4 alkyl or C1-C4 alkoxy radical or an xe2x80x94NO2 radical;
Xxe2x88x92represents an anion preferably selected from chloride, iodide, methyl sulphate, ethyl sulphate, acetate and perchlorate;
with the provisos that,
if R4 represents a C1-C4 alkyl radical and Z represents a sulphur atom, R3 does not represent a hydrogen atom;
if R5 represents Oxe2x88x92, then r represents zero;
if K or P or M represent C1-C4 xe2x80x94N-alkyl Xxe2x88x92, then R6 or R7 is other than a hydrogen atom;
if K represents xe2x80x94NR5(Xxe2x88x92)r, then Mxe2x95x90Pxe2x95x90xe2x80x94CH; xe2x80x94CR;
if M represents xe2x80x94NR5(Xxe2x88x92)r, then Kxe2x95x90Pxe2x95x90xe2x80x94CH; xe2x80x94CR;
if P represents xe2x80x94NR5(Xxe2x88x92)r, then Kxe2x95x90M and represent xe2x80x94CH or xe2x80x94CR;
if Z represents xe2x80x94NR2 and R2 represents a C1-C4 alkyl radical, then at least one of the radicals R1, R3 or R4 of A2 is other than a C1-C4 alkyl radical;
the symbol B represents:
(a) a group of structure B1 below: 
in which structure B1,
R8 represents a hydrogen atom, a halogen atom selected from chlorine, bromine, iodine and fluorine, a C1-C4 alkyl or C1-C4 alkoxy radical, a radical xe2x80x94OH, xe2x80x94NO2, xe2x80x94NHR11, xe2x80x94NR12R13 or xe2x80x94NHCO(C1-C4)alkyl radical or forms, with R9, a 5- or 6-membered ring which may or may not contain one or more hetero atoms selected from nitrogen, oxygen and sulphur;
R9 represents a hydrogen atom, a halogen atom selected from chlorine, bromine, iodine and fluorine, or a C1-C4 alkyl or C1-C4 alkoxy radical, or forms, with R10 or R11, a 5- or 6-membered ring which may or may not contain one or more hetero atoms selected from nitrogen, oxygen and sulphur;
R10 represents a hydrogen atom, an xe2x80x94OH radical, a radical xe2x80x94NHR11 or a radical xe2x80x94NR12R13;
R11 represents a hydrogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl or
C2-C4 polyhydroxyalkyl radical or a phenyl radical;
R12 and R13, which may be identical or different, represent a C1-C4 alkyl radical or a
C1-C4 monohydroxyalkyl or C2-C4 polyhydroxyalkyl radical;
(b) a 5- or 6-membered nitrogenous heterocyclic group which can contain other hetero atoms and/or carbonyl groups and which can be substituted with one or more
C1-C4 alkyl, amino or phenyl radicals, and in particular a group of structure B2 below: 
in which structure B2,
R14 and R15, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a phenyl radical; 
Y represents a xe2x80x94COxe2x80x94 radical or a radical
n=0 or 1, where, when n represents 1, U represents a xe2x80x94COxe2x80x94 radical.
In the structures defined above, the C1-C4 alkyl or alkoxy group preferably represents methyl, ethyl, butyl, methoxy or ethoxy.
The cationic direct dyes of formula (I) which can be used in the dye compositions in accordance with the invention are known compounds and are described, for example, in patent applications FR-2,189,006, FR-2,285,851 and FR-2,140,205 and its Certificates of Addition, the disclosures of all of which are specifically incorporated by reference herein.
Among the cationic direct dyes of formula (I) which can be used in the dye compositions in accordance with the invention, those of formula (I) in which the symbol A represents structure A3 while the symbol B represents structure B1 or B2 are particularly preferred.
Among these compounds, preferred compounds include the compounds of structures (I)1 to (I)77 below: 
The cationic direct dye(s) used according to the invention preferably represent(s) from about 0.001 to about 10% by weight relative to the total weight of the dye composition, and even more preferably from about 0.005 to about 5% by weight relative to this weight.
(ii) The cationic or amphoteric substantive polymer which can be used according to the present invention is selected from:
(1) dimethyidiallylammonium halide homopolymers and copolymers;
(2) methacryloyloxyethyltrimethylammonium halide homopolymers and copolymers;
(3) polyquaternary ammonium polymers chosen from those described below;
(4) vinylpyrrolidone copolymers containing methacrylamidopropyltrimethylammonium or methylvinylimidazolium units; and
(5) mixtures thereof.
The substantive nature, i.e., the ability to be deposited on the hair, of the polymers used according to the invention is determined conventionally using the test described by Richard J. Crawford, Journal of the Society of Cosmetic Chemists, 1980, 31-(5)-pages 273 to 278 (development by Red 80 acidic dye).
Among the substantive polymers of the methacryloyloxyethyltrimethylammonium halide homopolymer and copolymer type which can be used according to the invention, preferred polymers include the products referred to in the CTFA dictionary (5th edition, 1993) as xe2x80x9cPolyquaternium 37xe2x80x9d, xe2x80x9cPolyquaternium 32xe2x80x9d and xe2x80x9cPolyquaternium 35xe2x80x9d. xe2x80x9cPolyquaternium 37xe2x80x9d corresponds to the crosslinked poly(meth-acryloyloxyethyltrimethylammonium chloride) homopolymer, as a 50% dispersion in mineral oil, sold under the name Salcare SC95 by the company Allied Colloids. xe2x80x9cPolyquaternium 32xe2x80x9d corresponds to the crosslinked copolymer of acrylamide and of methacryloyloxyethyltrimethylammonium chloride (20/80 by weight), as a 50% dispersion in mineral oil, sold under the name Salcare SC92 by the company Allied Colloids. xe2x80x9cPolyquaternium 35xe2x80x9d corresponds to the methosulphate of the copolymer of methacryloyloxyethyltrimethylammonium and of methacryloyloxyethyidimethylacetylammonium, sold under the name Plex 7525L by the company Rohm GmbH.
Preferred substantive polymers of the dimethyldiallylammonium halide polymer type used according to the invention include:
dimethyldiallylammonium chloride homopolymers such as the one sold under the name xe2x80x9cMerquat 100xe2x80x9d by the company Merck;
copolymers of diallyldimethylammonium chloride and of acrylic acid, such as the one in proportions of 80/20 by weight sold under the name Merquat 280 by the company Calgon;
the copolymers of dimethyldiallylammonium chloride and of acrylamide sold under the names Merquat 550 and Merquat S by the company Merck.
Preferred substantive polymers of the polyquaternary ammonium type used according to the invention include:
the polymers prepared and described in French patent 2,270,846 (the disclosure of which is specifically incorporated by reference herein), comprising repeating units corresponding to formula (II) below: 
especially those in which the molecular weight, determined by gel permeation chromatography, ranges from 9500 to 9900;
the polymers prepared and described in French patent 2,270,846, comprising repeating units corresponding to formula (III) below: 
particularly those in which the molecular weight, determined by gel permeation chromatography, is about 1200;
the polymers described and prepared in U.S. Pat. Nos. 4,157,388, 4,390,689, 4,702,906 and 4,719,282 (the disclosures of which are specifically incorporated by reference herein) and comprising repeating units corresponding to formula (IV) below: 
in which p represents an integer ranging from 1 to 6 approximately, D can be absent or can represent a group xe2x80x94(CH2)rxe2x80x94COxe2x80x94 in which r represents a number equal to 4 or 7, the molecular mass of the said polymers preferably being less than 100,000, and more preferably less than or equal to 50,000; such polymers are sold in particular by the company Miranol under the names xe2x80x9cMirapol A15xe2x80x9d, xe2x80x9cMirapol AD1xe2x80x9d, xe2x80x9cMirapol AZ1xe2x80x9d and xe2x80x9cMirapol 175xe2x80x9d.
Among the vinylpyrrolidone polymers (PVP) containing methacrylamidopropyltrimethylammonium (MAPTAC) units, preferred polymers include those sold under the trade names Gafquat ACP 1011 and Gafquat HS 100 by the company ISP.
Preferred vinylpyrrolidone polymers (PVP) containing methylvinylimidazolium units, include:
the PVP/methylvinylimidazolium chloride copolymers sold under the names Luviquat FC 370, FC 550, FC 905 and HM 552 by the company BASF,
the PVP/methylvinylimidazolium chloride/vinylimidazole copolymer sold under the name Luviquat 8155 by the company BASF,
the PVP/methylvinylimidazolium methosulphate copolymer sold under the name Luviquat MS 370 by the company BASF.
The concentration of substantive polymer (ii) in the dye composition according to the invention can preferably range from about 0.01 to about 10% relative to the total weight of the dye composition, and more preferably from about 0.1 to about 5%.
The medium suitable for dyeing (or support) generally comprises water or a mixture of water and at least one organic solvent to dissolve the compounds that would not be sufficiently water-soluble. Preferred organic solvents include C1-C4 lower alkanols such as ethanol and isopropanol; aromatic alcohols such as benzyl alcohol, as well as similar products and mixtures thereof.
The solvents can be present in proportions preferably ranging from about 1 to about 40% by weight relative to the total weight of the dye composition, and even more preferably from about 5 to about 30% by weight.
The pH of the dye composition in accordance with the invention generally ranges from about 2 to about 11, and preferably from about 5 to about 10. The pH can be adjusted to the desired value using acidifying or basifying agents usually used for dyeing keratin fibres.
Among the acidifying agents, examples include inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid or lactic acid, and sulphonic acids.
Examples of basifying agents include aqueous ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamine and derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula (V) below: 
in which W is a propylene residue optionally substituted with a hydroxyl group or a C1-C6 alkyl radical; R16, R17, R18 and R19, which may be identical or different, represent a hydrogen atom or a C1-C6 alkyl or C1-C6 hydroxyalkyl radical.
In addition to the cationic direct dye(s) (i) defined above, the dye composition in accordance with the invention can contain one or more additional direct dyes which may be selected, for example, from nitrobenzene dyes, anthraquinone dyes, naphthoquinone dyes, triarylmethane dyes, xanthene dyes and azo dyes which are non-cationic.
When intended for oxidation dyeing, in addition to the cationic direct dye(s) (i), the dye composition in accordance with the invention comprises one or more oxidation bases selected from the oxidation bases conventionally used for oxidation dyeing, for example, para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases.
When it is (they are) used, the oxidation base(s) preferably represent(s) an amount ranging from about 0.0005 to about 12% by weight relative to the total weight of the dye composition, and even more preferably from about 0.005 to about 6% by weight relative to this weight.
When intended for oxidation dyeing, in addition to the cationic direct dye (i) and the substantive polymer (ii) as well as oxidation bases, the dye composition in accordance with the invention can also contain at least one coupler so as to modify or enrich with glints the shades obtained using the cationic direct dye(s) (i) and the oxidation bases.
The couplers which can be used in the dye composition in accordance with the invention can be selected from the couplers used conventionally in oxidation dyeing, for example, meta-phenylenediamines, meta-aminophenols, meta-diphenols and heterocyclic couplers.
When it is present, the at least one coupler preferably represents an amount ranging from about 0.0001 to about 10% by weight relative to the total weight of the dye composition, and even more preferably from about 0.005 to about 5% by weight relative to this weight.
The dye composition in accordance with the invention can also contain various adjuvants conventionally used in compositions for dyeing the hair, such as antioxidants, penetrating agents, sequestering agents, fragrances, buffers, dispersing agents, surfactants, film-forming agents, ceramides, preserving agents, screening agents and opacifiers.
Needless to say, a person skilled in the art will take care to select this or these optional complementary compound(s) such that the advantageous properties intrinsically associated with the dye composition according to the invention are not, or are not substantially, adversely affected by the addition(s) envisaged.
The dye composition according to the invention can be in various forms, such as in the form of liquids, shampoos, creams or gels or any other form suitable for dyeing keratin fibres, particularly human hair. The dye composition can be obtained by mixing, at the time of use, a composition, which may be in pulverulent form, comprising the cationic dye(s) with a composition containing the specific substantive polymer(s).
When the combination of the cationic direct dye (i) and the substantive polymer (ii) according to the invention is used in a composition intended for oxidation dyeing, i.e., one or more oxidation bases are used, optionally in the presence of one or more couplers, or when it is used in a composition intended for lightening direct dyeing, then the dye composition in accordance with the invention further comprises at least one oxidizing agent selected, for example, from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulphates, and enzymes such as peroxidases, laccases and two-electron oxidoreductases. The use of hydrogen peroxide or enzymes is particularly preferred.
Another subject of the invention is a process for dyeing keratin fibres, especially human keratin fibres such as the hair, using the dye composition as defined above.
According to a first variant of this dyeing process in accordance with the invention, at least one dye composition as defined above is applied to the fibres, for a period sufficient to develop the desired coloration, after which the fibres are rinsed, optionally washed with shampoo, rinsed again and dried.
The time required to develop the coloration on the keratin fibres generally ranges from 3 to 60 minutes and even more precisely from 5 to 40 minutes.
According to a second variant of this dyeing process in accordance with the invention, at least one dye composition as defined above is applied to the fibres, for a period sufficient to develop the desired coloration, without final rinsing.
According to one specific embodiment of this dyeing process, and when the dye composition in accordance with the invention contains at least one oxidation base and at least one oxidizing agent, the dyeing process includes a preliminary step which comprises separately storing, on the one hand, a composition (A1) comprising, in a medium suitable for dyeing, at least one cationic direct dye (i) as defined above and at least one oxidation base, and, on the other hand, a composition (B1) comprising, in a medium suitable for dyeing, at least one oxidizing agent, and then in mixing them together at the time of use, after which this mixture is applied to the keratin fibres, composition (A1) or composition (B1) containing the cationic or amphoteric substantive polymer (ii) as defined above.
According to another specific embodiment of this dyeing process, and when the dye composition in accordance with the invention contains at least one oxidizing agent, the dyeing process includes a preliminary step which comprises separately storing, on the one hand, a composition (A2) comprising, in a medium suitable for dyeing, at least one cationic direct dye (i) as defined above, and, on the other hand, a composition (B2) comprising, in a medium suitable for dyeing, at least one oxidizing agent, and then in mixing them together at the time of use, after which this mixture is applied to the keratin fibres, composition (A2) or composition (B2) containing the cationic or amphoteric substantive polymer as defined above.
Another subject of the invention is a multi-compartment dyeing device or xe2x80x9ckitxe2x80x9d or any other multi-compartment packaging system, a first compartment of which contains composition (A1) or (A2) as defined above and a second compartment of which contains composition (B1) or (B2) as defined above. These devices can be equipped with means for delivering the desired mixture onto the hair, such as the devices described in patent FR-2,586,913, the disclosure of which is specifically incorporated by reference herein, in the name of the L""Orxc3xa9al.
The present invention is further illustrated by the following examples which are designed to teach those of ordinary skill in the art how to practice the invention. The following examples are intended to illustrate the invention without limiting its scope.